Calculation of radiative transition probabilities and radiative recombination rate coefficients for H2, OH, H 2+ and OH+ molecules

A method is presented to calculate the radiative transition probabilities and the radiative recombination rate coefficients between electronic molecular states. Total transition probabilities are determined from vibrational transition probabilities without considering the detailed rotational structure of the molecular electronic states. Radiative recombination rate coefficients are obtained from the computation of vibrational photo-ionisation cross sections. Concerning spontaneous emission, Lyman (B → X) and Werner (C → X) band systems of H₂ and Meinel (A → X), (B → A) and (B → X) band systems of OH are investigated. For radiative recombination, transitions between H₂⁺ (X) and H₂(X), and between OH⁺(X, a, A, b, and c) and OH(X) are considered. Transition probabilities and recombination rate coefficients are calculated as a function of temperature in the range 1500–15 000 K.     

Cross section and rate coefficient calculations for electron impact excitation, ionisation and dissociation of the X 1Σg+, c 3Πu, a 3Σ g+, e 3Σu+ and B′1Σu+ states of H2

The weighted total cross section (WTCS) theory has been applied to the electron-H₂ collision to obtain excitation, ionisation and dissociation cross section and rate coefficients of the X ¹S_g⁺^{1}\!\Sigma _{g}^{+}, c ³P_u^{3}\!\Pi _{u}, a ³S_g⁺^{3}\!\Sigma _{g}^{+}, e $^{3}\!\Sigma _{u}^{+}$^{3}\!\Sigma _{u}^{+} and B^{′ 1}S_u⁺^{1}\!\Sigma _{u}^{+} states. Calculation has been performed in the temperature range 1500 K–15000 K. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. Thermal equilibrium results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) = a (θ^b) exp(-c/θ).     

The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

Study of inclusive strange-baryon production and search for pentaquarks in two-photon collisions at LEP

Measurements of inclusive production of the Λ, Ξ^- and Ξ^*(1530) baryons in two-photon collisions with the L3 detector at LEP are presented. The inclusive differential cross sections for Λ and Ξ^- are measured as a function of the baryon transverse momentum, p_t, and pseudo-rapidity, η. The mean number of Λ, Ξ^- and Ξ^*(1530) baryons per hadronic two-photon event is determined in the kinematic range 0.4 GeV<p_t<2.5 GeV, |η|<1.2. Overall agreement with the theoretical models and Monte Carlo predictions is observed. A search for inclusive production of the pentaquark θ⁺(1540) in two-photon collisions through the decay θ⁺→pK⁰ _S is also presented. No evidence for production of this state is found.     

Influence of covalence and anion symmetry on the structure of small metal hydroxide clusters: Sodium versus silver hydroxide

An ab initio study of the Na_n(OH)_n, Na_n(OH)_n-1 ⁺, Ag_n(OH)_n, and Ag_n(OH)_n-1 ⁺ clusters with n up to four is presented. The results of this study show that, in accordance with experimental observations, the sodium hydroxide clusters are almost purely ionic, while the Ag-O bond exhibits a significant covalent character. The perturbation caused by the non-spherical OH^- group relatively to an atomic anion, as well as the influence on structures and energies of the covalent character of the metal-oxygen bond are determined. The appearance of metal-metal bonds in the silver hydroxide clusters is also discussed. Finally, the theoretical results obtained on the Na-OH clusters are compared to experimental results available on the dissociation of the Na_n(OH)_n-1 ⁺ clusters. Received 9 August 1999 and Received in final form 1st December 1999     

Molecular orientation dependence of ortho-para H2 conversion on Fe(OH)3 cluster induced by hyperfine contact interaction

We investigate the molecular orientation dependence of the (o)rtho-(p)ara H₂ conversion on Fe(OH)₃ cluster. Taking Fermi's contact interaction as perturbation, we find that the o-p H₂ conversion yield for the molecular orientation angle θ= 10^○ with respect to the surface normal is larger than that for θ= 70^○.     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Linewidth studies on Cd+ 636.0 nm and 537.8 nm lines excited in a He-Cd hollow cathode discharge

Hollow cathode (HC) lasers usually operate in a single axial mode without any optical selection. This is attributed to the large homogeneous linewidth of the gain curve due to the relatively high filling pressure of these lasers. Collisional and Doppler broadening (Δν_C and Δν_D) of the Cd⁺ 636 nm and Cd⁺ 538 nm lines (laser transitions of the HeCd⁺ laser) excited in a HC discharge tube were determined using a Fabry–Perot interferometer technique. It was found that in the pressure range 7–25 mbar Δν_D was nearly constant, while, as expected, Δν_C increased linearly with pressure. The broadening constants were α(636 nm)= (47±2) MHz/mbarand α(538 nm)=(11.8±0.5) MHz/mbar. The first constant is large enough to explain single-mode operation of the red HeCd⁺ laser; but in the case of the green laser, the exact reason for the single-mode operation remained unclear. Received: 23 November 2000 / Revised version: 30 March 2001 / Published online: 7 June 2001     

Examining the redox and formate mechanisms for water–gas shift reaction on Au/CeO2 using density functional theory

We perform DFT calculations to investigate the redox and formate mechanisms of water–gas-shift (WGS) reaction on Au/CeO₂ catalysts. In the redox mechanism, we analyze all the key elementary steps and find that the OH cleavage is the key step. Three possible pathways of OH cleavage are calculated: (1) OH_ad^″+*^′→H_ad^′+O_ad^″; (2) H_ad^′+OH_ad^″→H₂(g)+O_ad^″+*^′; and (3) OH_ad^″+OH_ad^″→2O_ad^″+H₂(g) (*′: the free adsorption sites on the oxides; ad′: adsorption on the metal; ad″: adsorption on the oxide, respectively). In the formate mechanism, we identify all the possible pathways for the formation and decomposition of surface formates in the WGS reaction. It is found that there is a shortcoming in the redox and formate mechanisms which is related to surface oxygen reproduction. Four possible pathways for producing surface oxygen are studied, and all the barriers of the four pathways are more than 1 eV. Our results suggest that the processes to reproduce surface oxygen in the reaction circle are not kinetically easy.     

Synthesis and ionic conduction of apatite-type materials

Apatite is a mineral with general formula M₁₀(XO₄)₆Z₂, where M are metallic elements such as Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ln³⁺ etc.; X=P, V, S, Si, Ge, Re, Cr etc; Z=F⁻, Cl⁻, I⁻, OH⁻, O²⁻, S²⁻ etc. Some materials with apatite structure (S.G. P6₃/m) exhibit quite high cationic (Li⁺, H⁺ etc.) and/or anionic (F⁻, Cl⁻ etc.) conduction. Recently, it was reported that some rare earth silicates, e.g., La₁₀(SiO₄)₆O₃, exhibit quite high oxide-ion conductivity. In this paper, we discuss chemical composition, structure, synthetic procedure and ionic conduction of apatite-type materials. Recent improvements are briefly reviewed. High ionic conductivity has been observed for both cation deficient, oxygen stoichiometric La_9.33(SiO₄)₆O₂ and cation stoichiometric, oxygen excess La₁₀(SiO₄)₆O₃ compositions. Grain boundary conductivity is usually low, which tends to dominate the impedance response. The resistance, particularly the grain boundary resistance is also found to depend on pO₂. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Photodetachment of H- in a static electric field

We derive a formula using closed-orbit theory for the photodetachment cross-section of H^- in the presence of a static electric field when there is an arbitrary angle θ_L between the laser polarization direction and the static electric field. This formula generalizes the previous result for laser polarization parallel to the static electric field, the effect of laser polarization direction appears as a factor cos²(θ_L) in the amplitude of the oscillation. A photodetachment cross-section formula valid above and below detachment threshold is proposed.     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.     

The infrared and Raman spectra of solid CsSbF 5OH and CsSbF 4(OH)2

The infrared and Raman spectra of solid CsSbF ₅OH and CsSbF ₄(OH)₂ have been studied to determine the effect of replacing one or more F^--ions by OH^--ions in the SbF^-₆-ion. The results have been obtained in the frequency ranges where the Sb-F and Sb-OH stretching modes are known to occur. The spectra are in agreement with a low site symmetry for the SbF ₅OH^--ion in CsSbF ₅OH but are largely inconclusive as to whether the OH-groups in CsSbF ₄(OH)₂ have cis- or trans-symmetry.     

Electron screening in backward elastic scattering

Abstact: The elastic scattering cross sections, σ (E,θ), for the systems He+Ta and He+W have been measured at θ_lab=165° and E _lab=76.1 keV to 3.988 MeV using targets with a thickness of a few atomic layers. The results are smaller than the results given by the Rutherford scattering law, σ_R(E,θ), due to the effects of electron screening and can be described by σ(E,θ)/σ_R(E,θ)=(1+U_e/E)⁻¹, where U _e is an atomic screening potential energy. The deduced average value, U _e=28 ± 3 keV, is consistent with the Moliére- and Lenz-Jensen-models as well as electron binding energies. Received: 25 May 1998     

Measurement of OH spatially resolved spectrum in a wire-plate pulsed streamer discharge

In this study, spatially resolved measurements of the emission intensity of OH (A²Σ↦X²Π, 0-0) and the vibrational temperature of N₂ (C) have been performed during a positive pulsed streamer discharge with a wire-plate electrode configuration at atmospheric pressure. The effects of pulse peak voltage, pulse repetition rate and the added O₂ flow rate on the spatial distributions of the emission intensity of OH (A²Σ↦X²Π, 0-0) and the vibrational temperatures of N₂ (C) perpendicular to the wire in the direction towards the plate (in the radial direction) are investigated. It has been found that the emission intensity of OH (A²Σ↦X²Π, 0-0) increases with increasing pulse peak voltage and pulse repetition rate and decreases with increasing the distance from the wire electrode. When the different oxygen flows are added in N₂ and H₂O mixture gas, the emission intensity of OH (A²Σ↦X²Π, 0-0) decreases with increasing the flow rate of oxygen. The vibrational temperature of N₂ (C) is nearly independent of pulsed peak voltage and pulsed repetition rate, but increases with increasing the added O₂ flow rate and keeps almost constant in the radial direction under the present experimental conditions. This measurement plays a crucial role in understanding the discharge characters of pulsed streamer discharge and establishing the molecule reaction dynamics model of pulsed streamer discharge.     

Rapid growth of ternary eutectic under high undercooling conditions

~~Rapid growth of ternary eutectic un der high undercooling conditions1.Offerman, S.E., Dijk, N.H., Sietsma, J.et al., Grain nucleation and growth during phase transformations, Science, 2002, 298: 1003-1005. 2.Warren, J.A., Langer, J.S., Prediction of dendritic spacings in a directional-solidification experiment, Phys.Rev.E, 1993, 47: 2702-2712. 3.Cao, C.D., Wang, N., Wei, B., Containerless rapid solidification of undercooled Cu-Co peritectic alloys, Science in China, Ser.A, …     

Mössbauer study of ultrafine amorphous Fe−B alloys

The chemical composition of ultrafine amorphous Fe−B powders prepared by a chemical reduction depends on the mixed molar ratio of KBH₄ to Fe ions. We propose the following reaction processes for the formation of ultrafine Fe−B powders: (1) 4Fe²⁺+2BH₄₋+6OH⁻→2Fe₂B+6H₂O+H₂ and (2) 4Fe²⁺+2BH₄₋+7OH⁻→2Fe₃B+Fe+BO₂+5H₂O+5/2H₂.     

Study of charmonia in four-meson final states produced in two-photon collisions

We report measurements of charmonia produced in two-photon collisions and decaying to four-meson final states, where the meson is either a charged pion or a charged kaon. The analysis is based on a 395 fb^-1 data sample accumulated with the Belle detector at the KEKB electron–positron collider. We observe signals for the three C-even charmonia η_c(1S), χ_c0(1P) and χ_c2(1P) in the π⁺π^-π⁺π^-, K⁺K^-π⁺π^- and K⁺K^-K⁺K^- decay modes. No clear signals for η_c(2S) production are found in these decay modes. We have also studied resonant structures in charmonium decays to two-body intermediate meson resonances. We report the products of the two-photon decay width and the branching fractions, , for each of the charmonium decay modes. PACS 13.25.Gv; 13.66.Bc; 14.40.Gx